Production of vat dyestuffs



United States Patent PRODUCTION OF VAT DYESTUFFS Riitger Neelf and HeinzWerner Schwechten, Leverkusen- .llayerwerk, Germany, assignors toFarbenfabriken flay er Aktiengese'llschaft, Leverkusen, Germany, acorporation of Germany No Drawing. Application May 27, .1954

Serial No. 432,915

Claims priority, application Germany May 29, 1953 7 Claims. 01. 260-368)This invention relates .to .new vat dyestuffs and to meth ads forpreparing the same.

.In German Patent 343,252 there is describeda dark vatdyestufi havingthe following formula:

anthraquinone which are useful to the invention include.

the halogen-substitution products, such as 6411101105 7- chloro-,6.7-dichloroand 6(7)-chloro-1-amino-2-methyl-' anthraquinone, the 6- and7-al'kyland arylsulfones, and the 6 and 7-sulfonamido derivatives.4-acylaminoand Sacylamino-1eamino-.2-methyl-anthraquinones have alsoproven to the suitable starting materials for preparing the dyestuffs ofthe invention.

XI Alternatively, 1 mol of 1.4- or'1..'5-diamino-anthraquinone-2-aldehyde may be reacted with /2 .mol ofhydrazine and the reaction product acylated "with suitable :acidhalides. Thus, (the same dyestuffs are obtained as in the reaction ofhydrazine with the azomethines formed by oxidation of 4-acylaminoor.S-acyIamino-l-amino-Z- methyl-anthraquinone with nitrobenzene.

Another method for preparing the novel dyestufls of this inventioncomprises reacting nuclearly substituted 1-amino-anthraquinone-2-aldehydes or the 1.2-anthraquinone-3-isoxazolesobtainable therefrom with hydrazine.

It is of course possible to use a mixture of two differently substitutedazomethines and aldehydes, respectively, in the reaction with hydrazine.In this case asymmetric azines are formed.

The invention is further illustrated, but not limited, by the folowingexamples in which all parts are by weight:

Example I 20 parts of 6-chloro-1-amino-2-methyl-anthraquinone, 10 .partsof potassium carbonate, 4 parts of aniline, and 120 parts ofnitrobenzene are refluxed for 6 hours. The reaction mixture is filteredwith suction at 170 C. The phenyl-azomethines of6-chloro-l-amino-anthraquinoneexcellent fastne ss to light -and tochlorine.

dissolves in concentrated sulfuric acid 2-aldehyde crystallizes from thefiltrate on cooling in the form of blue-red prismatic needles which arefiltered 01f with suction and freed of nitrobenzene in the usual man-The *azlomethines dissolve in concentrated suliuri'c acid to :give anolive-colored solution. When adding paraformaldehyde in the cold '21gray-blue solution is obtained which becomes green on heating.

50 parts of the azomethines and 14.5 parts of a 22.9% aqueous solutionof hydrazine hydrate are refluxed for 2 hours in 1500 parts of glacialacetic acid. The conversion of the blue-red prism ofthe azomethines intothe needles of the azine is followed'microscopically. When the reactionis complete the precipitate is filtered off with suction and washed withsome glacial acetic acid. The azine whichhas the formula to give an'olivecolored solution. However, when paraformaldehyde is added in thecold a blue green solution is obtained which gets blue. on heating.Cotton is dyed from a red-blue vat in strong red-violet shades. Thefastness to light of the dyeings is much *greater'than those obtainedwith "the azine described in German Patent 343,252.

The same dye maybe obtained by reacting6-chloro-laminomnthraquinoneasaldehyde or'G-chIoro-anthraquinone-1.2-isoxa'zo1e with hydrazine hydrate.

Example 2 50 parts of .l-aminor'2-methyl-4-benzoylamino anthraquinone,25 parts of potassium carbonate, and 10 par-ts of aniline are refluxedin 300 parts of nitrobenzene until a sampledissolves in pyridine with aclear blue color. The reactionmixture is filtered while hot. On coolingthe phenyl-azomethines ofl-amino-4-benzoylamino-anthraquinone-Z-aldehyde.crystallizes from thefiltrate in beau-- tiful dark blue prisms. The crystals dissolve inconcentrated sulfuric acid to give a green'ish-yellow solution. Onaddition of paraformaldehyde in the cold the color changes toblue-green. On heating the color changes from blue-green to a dullviolet.

9 parts of the phenyl-azomethines thus obtained are mixed with 2.2 partsof a 22.9% .aqueous solution of hydrazine hydrate and 300 parts ofglacial acetic acid and the solution isrefluxed for 4 hours. The darkblue prisms of the azomethines are hereby converted into greenish-blueneedles of the azine. This conversion may be followed microscopically.The azine having the formula N in;

doom. $0.05. is worked up as described in Example 1. Its reaction withsulfuric acid and formaldehyde is similar to that of the .azomet-hines.The azine is poorly soluble in .highboiling organic solvents. Cotton isdyed from a bluishviolet vatin greenish-blue shades. The dyeings exhibitIn an analogous manner dyes from 4-(p-chlorobenzoyl)-aminoand4-(p-methoxybenzoyl)-amino-1-amino- Z-methyl-anthraquinone may beobtained. The shades of these dyes are more greenish than that of theabove azine which is not substituted in the benzoyl group.

Example 3 40 parts of 1 amino-2-methyl-5-benzoylamino-anthra-' quinone,20 parts of potassium carbonate, and 8 parts of aniline are refluxed for1%-2 hours into 240 parts of nitrobenzene. The reaction mixture isfiltered ofi by suction at 170 C. The prismatic needles of thephenylazomethines of 1-amino-S-benzoylamino-anthraquinone- 2-aldehydewhich crystallize on cooling are recovered in the usual manner. Thecolor of the solution of the prod-- net in concentrated sulfuric acid isyellow. The reaction with formaldehyde gives a blue color in the coldand a.

green color when heated- 1 55 parts of the azomethines, and,3 parts ofhydrazine hydrate are refluxed for 4 hours in 1600 parts of glacialacetic acid. On cooling the azine, which crystallizes from the boilingmixture in violet needles, is filtered off with suction and washed withsome glacial acetic acid. The azine having the formula NH; NN NH: O

dyes cotton in very full red-violet shades.

Example 4 10 parts of 1.4-diamino anthraquinone-il-aldehyde and 3.2parts of a 22.9% aqueous solution of hydrazine hydrate are refluxed for2 hours in 350 parts of glacial acetic acid. The azine crystallizing ingray-blue needles is filtered ofi with suction, Washed .with glacialacetic acid,- and dried.

7.2 parts of the azine in 6 0 parts'of nitrobenzene are acylated byadding dropwise 5.9 parts of 'm-trifluormethylbenzoyl chloride at 95 C.A' product is obtained which crystallizes in blue needles and may beisolated in theusual manner. The dyestufi whichhas the formula is poorlysoluble in organic solvents. From quinoline it crystallizes in blueprisms which dissolve in concentrated sulfuric acid to give a greensolution.- On addition of paraformaldehyde in the cold thecolor of thesolution changes to blue-green. When heating the color becomes dullviolet. Cotton is dyed from a bluish-violet vat in full blue shades ofextraordinary wash and light fastness.

7 Example I zoylamino-anthraquinone 2 aldehyde --phenyl azomethines and1.44parts of a 22.9% aqueous solution of hydrazine hydrate are refluxedin 180 parts of glacial- 1 a 4, P i acetic acid until unchangedazomethines can no longer be detected. The azine of the formula i) NH:.E-N NH: 0

NH NH $0.0M; a a is isolated in the usual way. It dissolves inconcentrated sulfuric acid with a greenish-yellow color which onaddition of paraformaldehyde changes to green in the cold and to a dullgreen when heated. Cotton is dyed from a bluish-violet vat in strongblue-gray shades.

Example 6 p 47.5 parts of1-amino-4-p-methoxy-benzoylamino-authraquinone-2-aldehyde-phenyl-azomethines,32.6 parts of a 6 chloro 1 amino anthraquinone 2aldehydephenyl-azomethines and 21.5 parts of a 22.9% aqueous solutionofv hydrazine hydrate are refluxed for several hours 'in' 3000 parts ofglacial acetic acid. The product is filtered 01f with suction and freedof glacial acetic acid. The dyestutr' of the formula O NH: NN NHzOdissolves in concentrated sulfuric acid with a brownish-i v Q 3' partsof 1 arnino-5-benzoylamino-anthraquinone-2-ialdehyde-phenyl-azomethines', 3 parts of l-amino-4-be'n- 0 N H: NN NH: O

w imam g H $0.0m; "1 10,0 11, The product is filtered off with suctionand fr'eedof the solvent. The dyestufi dyes cotton from a blue vat instrong, marine-blue shades having excellent fastness properties.

N 11ml a which are members selected from the group consisting of'anthraquinone dyestuffs nuclearly substituted in both anthraquinoneradicals with chlorine and an anthraquinone dyestufi nuclearlysubstituted in one anthraquinone radical with a member of the groupconsisting of benzoyl amino radicals substituted with a member selectedfrom the group consisting of chlorine, alkoxyl, and trifluor methylgroups and anthraquinone dyestufis nuclearly substituted in bothanthraquinone radicals with a member of the group consisting of benzoylamino radicals and benzoyl amino radicals substituted with a memberselected from the group consisting of chlorine, alkoxyl, and trifluormethyl groups.

2. The anthraquinone dyestufi having the following formula:

3. The anthraquinone dyestutf having the following formula:

NH: ITT-N N H:

4. The anthraquinone dyestutf having the following formula:

3 NH: NN NH2 f) O NH NH I 50.0KB; O.C H

5. The anthraquinone dyestuif having the following formula:

OCH: CH;

6. The anthraquinone dyestuff having the following formula:

7. The anthraquinone dyestufi having the following formula:

References Cited in the file of this patent UNITED STATES PATENTS1,285,727 Kalischer Nov. 26, 1918 1,881,697 Kunz Oct. 11, 1932 2,230,574Mieg et a1. Feb. 4, 1941 FOREIGN PATENTS 642,592 Great Britain Sept. 6,1950 OTHER REFERENCES Georgievics: Dye Chemistry, 1920, page 255.

1. AS ANTHRAQUINONE DYESTUFFS, DERIVATIVES OF